JP7072511B2 - Organometallic compounds - Google Patents
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- JP7072511B2 JP7072511B2 JP2018542759A JP2018542759A JP7072511B2 JP 7072511 B2 JP7072511 B2 JP 7072511B2 JP 2018542759 A JP2018542759 A JP 2018542759A JP 2018542759 A JP2018542759 A JP 2018542759A JP 7072511 B2 JP7072511 B2 JP 7072511B2
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- C23C16/45525—Atomic layer deposition [ALD]
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45553—Atomic layer deposition [ALD] characterized by the use of precursors specially adapted for ALD
Description
本発明は、金属酸化物気相蒸着の前駆体として有用となり得る有機金属化合物に関する。本発明の有機金属化合物は、強いルイス塩基である配位子を1つ以上含む。本発明は、かかる化合物を触媒として使用した、オキシダントの存在下での金属酸化物低温気相蒸着にも関する。 The present invention relates to organometallic compounds that may be useful as precursors for metal oxide vapor deposition. The organometallic compound of the present invention contains one or more ligands that are strong Lewis bases. The present invention also relates to low temperature vapor deposition of metal oxides in the presence of oxidants using such compounds as catalysts.
トランジスタのサイズが縮小され続けていることから、SiO2及びその他の金属酸化物を高温で熱蒸着するための標準的方法の使用に問題が生じてきた。高温の使用は、いくつかの元素の拡散を引き起こす。この拡散は、トランジスタの基本的特性を変える。結果として、デバイスが損傷される。したがって、High-kを適用するための高品質SiO2及び金属酸化物の低温熱蒸着が好ましい。しかし、一般的に、プラズマアシスト蒸着は、その下にあるデバイス構造を損傷する可能性があることから、SiO2の熱(すなわち、高温)蒸着が好ましい。二酸化ケイ素(SiO2)は、シリコンマイクロエレクトロニクスデバイスにおいて一般的な誘電材料である。高品質のSiO2は、700~900℃でのケイ素の熱酸化によって形成されてきた。SiO2は、化学蒸着(CVD)による堆積も行われており、いくつかのこのようなアプローチは、プラズマ技術を利用する。しかし、CVDは高アスペクト比構造においてコンフォーマルではなく、トレンチ及びバイアスにボイド構造を示す。 The continued shrinking of transistor sizes has created problems with the use of standard methods for thermal vapor deposition of SiO 2 and other metal oxides at high temperatures. The use of high temperatures causes the diffusion of some elements. This diffusion changes the basic characteristics of the transistor. As a result, the device is damaged. Therefore, low temperature thermal deposition of high quality SiO 2 and metal oxides for applying High-k is preferred. However, in general, plasma-assisted vapor deposition is preferred for the thermal (ie, high temperature) deposition of SiO 2 as it can damage the underlying device structure. Silicon dioxide (SiO 2 ) is a common dielectric material in silicon microelectronic devices. High quality SiO 2 has been formed by thermal oxidation of silicon at 700-900 ° C. SiO 2 has also been deposited by chemical vapor deposition (CVD), and some such approaches utilize plasma technology. However, CVD is not conformal in high aspect ratio structures and exhibits void structures in trenches and biases.
原子層堆積(ALD)法は、コンフォーマル性及び薄膜成長の原子層制御を得るために使用できる。原子層堆積(ALD)は、逐次的な、自己制御型の表面反応に基づく成長方法である。酸化物、窒化物、及び種々の金属等の様々な材料が、ALDを用いて堆積されてきた。 Atomic layer deposition (ALD) methods can be used to obtain conformality and atomic layer control of thin film growth. Atomic layer deposition (ALD) is a sequential, self-regulating surface reaction-based growth method. Various materials such as oxides, nitrides, and various metals have been deposited using ALD.
その重要性にもかかわらず、SiO2のALDは実現が困難であった。SiCl4及びH2Oを使用するSiO2のALDは、高温(>325℃)及び大量の反応物質曝露(>109L(1L)10-6トル)を必要とする。NH3又はピリジンの使用により、室温に近い温度及び約103~104Lの曝露が可能になる。しかし、上記の方法によって発生する副生成物は、真空ラインの閉塞、アミン塩酸塩の薄膜への混入を引き起こす場合があり、そのため、薄膜の最終的な品質は極めて低い。 Despite its importance, the ALD of SiO 2 has been difficult to achieve. ALD of SiO 2 using SiCl 4 and H 2 O requires high temperature (> 325 ° C.) and heavy reactant exposure (> 109 L (1 L) 10-6 tolls). The use of NH 3 or pyridine allows exposure to temperatures close to room temperature and about 103-104 L. However, the by-products generated by the above method can cause blockage of the vacuum line and contamination of the amine hydrochloride into the thin film, so that the final quality of the thin film is extremely low.
しかし、これらの方法においてハロゲン化物を使用すると、堆積中に腐食性のHClが放出される。さらに、放出されたHClは、アミン触媒と反応して塩化物塩を形成し、膜汚染、ひいては低い膜品質を招く。 However, the use of halides in these methods releases corrosive HCl during deposition. In addition, the released HCl reacts with the amine catalyst to form chloride salts, leading to membrane contamination and thus poor membrane quality.
ハロゲン化物の使用を避けるため、SiO2のALDは、アルコキシシラン、アミノシラン及びイソシアナート等の様々な反応物質の使用、種々の触媒及び反応条件の使用を試みてきた。これらの方法は、大量の反応物質曝露を必要とする、長い蒸着時間や、堆積膜の汚染を生じるなど、多数の欠点に悩まされてきた。 To avoid the use of halides, the ALD of SiO 2 has attempted to use various reactants such as alkoxysilanes, aminosilanes and isocyanates, as well as various catalysts and reaction conditions. These methods have suffered from a number of drawbacks, including the need for large exposures to reactants, long deposition times and contamination of sedimentary membranes.
有機金属化合物の一分類が提供される。化合物は、式1の構造に相当し:
(A)x-M-(OR3)4-x
式中:
Aは、-NR1R2、-N(R4)(CH2)nN(R5R6)、-N=C(NR4R5)(NR6R7)、OCOR1、ハロ及びYからなる群から選択され;
R1及びR2は、R1及びR2のうちの少なくとも1つはH以外でなければならないことを条件として、独立して、H及び1~8個の炭素原子を有する環式又は非環式アルキル基からなる群から選択され;
R4、R5、R6及びR7は、独立して、H及び1~4個の炭素原子を有する非環式アルキル基からなる群から選択され;
Yは、少なくとも1個の窒素原子を含有する3員~13員の複素環式基からなる群から選択され;
R3は、1~6個の炭素原子を有する環式又は非環式アルキル基であり;
Mは、Si、Ge、Sn、Ti、Zr及びHfからなる群から選択され;
xは、1~3の整数であり;
nは、1~4の整数である。
A classification of organometallic compounds is provided. The compound corresponds to the structure of formula 1:
(A) x -M- (OR 3 ) 4-x
During the ceremony:
A is -NR 1 R 2 , -N (R 4 ) (CH 2 ) nN (R 5 R 6 ), -N = C (NR 4 R 5 ) (NR 6 R 7 ), OCOR 1 , halo and Y. Selected from the group consisting of;
R 1 and R 2 are independently cyclic or acyclic with H and 1-8 carbon atoms, provided that at least one of R 1 and R 2 must be other than H. Selected from the group consisting of formula alkyl groups;
R 4 , R 5 , R 6 and R 7 are independently selected from the group consisting of H and acyclic alkyl groups with 1 to 4 carbon atoms;
Y is selected from the group consisting of 3- to 13-membered heterocyclic groups containing at least one nitrogen atom;
R 3 is a cyclic or acyclic alkyl group having 1 to 6 carbon atoms;
M is selected from the group consisting of Si, Ge, Sn, Ti, Zr and Hf;
x is an integer from 1 to 3;
n is an integer of 1 to 4.
かかる化合物は、金属酸化物気相蒸着の前駆体として有用となり得る。本発明の化合物は、強いルイス塩基である配位子を1つ以上含む。代表的な塩基は、アセタート、ハロゲン化物並びにホスファゼン、アミジン及びグアニジンのような中性でプロトン親和性の高い含窒素種を含む。 Such compounds can be useful as precursors for metal oxide vapor deposition. The compounds of the present invention contain one or more ligands that are strong Lewis bases. Representative bases include acetate, halides and neutral, proton-friendly nitrogen-containing species such as phosphazene, amidine and guanidine.
これらの化合物は、CVD、ALD、プラズマアシストALD及びプラズマアシストCVD等の気相堆積プロセスの前駆体として有用となり得る。 These compounds can be useful as precursors for vapor deposition processes such as CVD, ALD, Plasma Assist ALD and Plasma Assist CVD.
有機金属化合物の一分類が提供される。化合物は、式1の構造に相当し:
(A)x-M-(OR3)4-x
式中:
Aは、-NR1R2、-N(R4)(CH2)nN(R5R6)、-N=C(NR4R5)(NR6R7)、OCOR1、ハロ及びYからなる群から選択され;
R1及びR2は、R1及びR2のうちの少なくとも1つはH以外でなければならないことを条件として、独立して、H及び1~8個の炭素原子を有する環式又は非環式アルキル基からなる群から選択され;
R4、R5、R6及びR7は、独立して、H及び1~4個の炭素原子を有する非環式アルキル基からなる群から選択され;
Yは、少なくとも1個の窒素原子を含有する3~13位の複素環式基からなる群から選択され;
R3は、1~6個の炭素原子を有する環式又は非環式アルキル基であり;
Mは、Si、Ge、Sn、Ti、Zr及びHfからなる群から選択され;
xは、1~3の整数であり;
nは、1~4の整数である。
A classification of organometallic compounds is provided. The compound corresponds to the structure of formula 1:
(A) x -M- (OR 3 ) 4-x
During the ceremony:
A is a group consisting of -NR 1 R 2 , -N (R 4 ) (CH 2 ) nN (R 5 R 6 ), -N = C (NR 4 R 5 ) (
R 1 and R 2 are independently cyclic or acyclic with H and 1-8 carbon atoms, provided that at least one of R 1 and R 2 must be other than H. Selected from the group consisting of formula alkyl groups;
R 4 , R 5 , R 6 and R 7 are independently selected from the group consisting of H and acyclic alkyl groups with 1 to 4 carbon atoms;
Y is selected from the group consisting of heterocyclic groups at
R 3 is a cyclic or acyclic alkyl group having 1 to 6 carbon atoms;
M is selected from the group consisting of Si, Ge, Sn, Ti, Zr and Hf;
x is an integer from 1 to 3;
n is an integer of 1 to 4.
かかる化合物は、金属酸化物気相蒸着の前駆体として有用となり得る。本発明の化合物は、強いルイス塩基である配位子を1つ以上含む。代表的な塩基は、アセタート、ハロゲン化物並びにホスファゼン、アミジン及びグアニジンのような中性でプロトン親和性の高い含窒素種を含む。 Such compounds can be useful as precursors for metal oxide vapor deposition. The compounds of the present invention contain one or more ligands that are strong Lewis bases. Representative bases include acetate, halides and neutral, proton-friendly nitrogen-containing species such as phosphazene, amidine and guanidine.
強塩基は、当該技術分野で使用される塩基の代表例であるNH3のような塩基よりもはるかに有効かつ効率的にSiO2の形成を触媒する。強塩基触媒の使用により、低温でのSiO2のCVD及びALDの蒸着が可能になる。さらには、高品質のSiO2膜も得られる。 Strong bases catalyze the formation of SiO 2 much more effectively and efficiently than bases such as NH 3 , which is a representative example of bases used in the art. The use of a strong base catalyst enables CVD of SiO 2 and deposition of ALD at low temperatures. Furthermore, a high quality SiO 2 film can also be obtained.
本発明の化合物は、原子層堆積(ALD)、化学気相堆積(CVD)、プラズマアシストALD及びプラズマアシストCVDのような化学相堆積のプロセスにおいて前駆体として有用となり得る。 The compounds of the present invention can be useful as precursors in chemical phase deposition processes such as atomic layer deposition (ALD), chemical vapor deposition (CVD), plasma-assisted ALD and plasma-assisted CVD.
本発明の化合物を上記プロセスに使用することは、当該技術分野において以前から知られているプロセスよりも低温(0~500℃)で蒸着を実施できるという利点がある。 The use of the compound of the present invention in the above process has the advantage that the vapor deposition can be carried out at a lower temperature (0 to 500 ° C.) than the processes previously known in the art.
反応が進行する温度範囲は、式1の化合物に結合する(NR1R2)x基の数を変える(すなわち、xを変える)ことによって、及び(NR1R2)基の性質を変えることによって、調節できる。 The temperature range in which the reaction proceeds is by changing the number of (NR 1 R 2 ) x groups attached to the compound of formula 1 (ie, changing x) and by changing the properties of the (NR 1 R 2 ) groups. Can be adjusted by.
反応温度は、0~500℃、より好ましくは100~350℃の範囲であってもよい。 The reaction temperature may be in the range of 0 to 500 ° C, more preferably 100 to 350 ° C.
強塩基配位子を式1の化合物に組み込むことにより、2成分(Si前駆体+触媒)を使用する当該技術分野のプロセスと比べて、より単純なプロセスが可能になり、曝露の均一性及び膜品質が改善される。
Incorporating the strong base ligand into the compound of
式1の化合物は、基材への適用を促進する揮発性及び安定性等の所望の特性を提供するように設計できる。これは、強塩基配位子A及びアルキル基(OR3)の数(x)及び同一性を調節することによって影響を受ける可能性がある。
The compounds of
本発明の化合物は、Mが、Si、Ge、Sn、Ti、Hf及びZrからなる群から選択される化合物を含む。好ましい化合物としては、Mが、Si、Ge及びSnからなる群から選択されるものが挙げられる。より好ましい化合物としては、MがSiのものが挙げられる。 The compounds of the present invention include compounds in which M is selected from the group consisting of Si, Ge, Sn, Ti, Hf and Zr. Preferred compounds include those in which M is selected from the group consisting of Si, Ge and Sn. More preferable compounds include those in which M is Si.
本発明の化合物は、R3が、1~6個の炭素原子を有する環式又は非環式アルキル基である化合物も含む。好ましい化合物は、R3が1~4個の炭素原子を有する直鎖又は分岐した低級アルキル基である化合物である。さらに他の好ましい化合物は、R3がメチル及びエチルからなる群から選択される化合物である。 The compounds of the present invention also include compounds in which R 3 is a cyclic or acyclic alkyl group having 1 to 6 carbon atoms. Preferred compounds are compounds in which R 3 is a linear or branched lower alkyl group having 1 to 4 carbon atoms. Yet another preferred compound is one in which R3 is selected from the group consisting of methyl and ethyl.
本発明の化合物としては、Aが、-NR1R2、-N(R4)(CH2)nN(R5R6)、-N=C(NR4R5)(NR6R7)、OCOR1、ハロ及びYからなる群から選択される化合物も挙げられる。好ましい化合物としては、Aがアセタート、テトラエチルグアニジニル、ジメチルエチレンジアミニル、ブロモ、ヨード及び-NR1R2基からなる群から選択されるものが挙げられる。より好ましい化合物としては、Aが-NR1R2基であるものが挙げられる。 In the compound of the present invention, A is -NR 1 R 2 , -N (R 4 ) (CH 2 ) nN (R 5 R 6 ), -N = C (NR 4 R 5 ) (NR 6 R 7 ). Also included are compounds selected from the group consisting of, OCOR 1 , halo and Y. Preferred compounds include those in which A is selected from the group consisting of acetate, tetraethylguanidineyl, dimethylethylenediaminyl, bromo, iodine and -NR 1 R2 groups. More preferable compounds include those in which A is -NR 1 R 2 groups.
その他の好ましい化合物は、R1及びR2が、独立して、H及び1~8個の炭素原子を有する環式又は非環式アルキル基からなる群から選択される化合物である。 Other preferred compounds are compounds in which R 1 and R 2 are independently selected from the group consisting of H and a cyclic or acyclic alkyl group having 1-8 carbon atoms.
本発明のより好ましい化合物としては、R1及びR2が、独立して、1~4個の炭素原子を有するアルキル基からなる群から選択されるものが挙げられる。本発明のその他の好ましい化合物としては、R1及びR2が、独立して、メチル、エチル及びイソブチルからなる群から選択されるものが挙げられる。 More preferred compounds of the invention include those in which R 1 and R 2 are independently selected from the group consisting of alkyl groups having 1 to 4 carbon atoms. Other preferred compounds of the invention include those in which R 1 and R 2 are independently selected from the group consisting of methyl, ethyl and isobutyl.
本発明の化合物は、Yが、少なくとも1個の窒素原子を含有する3~13位の複素環式ラジカルを表すものも含む。
The compounds of the present invention also include those in which Y represents a heterocyclic radical at
本発明の好ましい化合物としては、Yが、アジリジニル、アゼチジニル、ピロリジニル、ピロリル、ピペリジニル、ピリジニル、アゼパニル、又はアゼピニルのような基である化合物が挙げられる。 Preferred compounds of the present invention include compounds in which Y is a group such as aziridinyl, azetidinyl, pyrrolidinyl, pyrrolyl, piperidinyl, pyridinyl, azepanyl, or azepinyl.
本発明の更なる化合物としては、Yが少なくとも1個のその他のヘテロ原子を有するもの、例えば、オキサジリジニル、イミダゾリジニル、ピラゾリジニル、オキサゾリジニル、イソオキサゾリジニル、ピペラジニル、モルホリニル、イミダゾリル、ピラゾリル、オキサゾリニル、イソオキサゾリル、ジアジニル、又はオキサジニル基である化合物が挙げられる。 Further compounds of the invention include those in which Y has at least one other heteroatom, such as oxazilidinyl, imidazolidinyl, pyrazolidinyl, oxazolidinyl, isooxazolidinyl, piperazinyl, morpholinyl, imidazolyl, pyrazolyl, oxazolinyl, isooxazolyl. , Diazinyl, or a compound that is an oxadinyl group.
好ましい化合物は、Yが、ピロリジニル、アゼチジニル及びアジリジニルからなる群から選択される化合物である。 The preferred compound is a compound in which Y is selected from the group consisting of pyrrolidinyl, azetidinyl and aziridinyl.
本発明の化合物としては、R4、R5、R6及びR7が、独立して、H及び1~4個の炭素原子を有する非環式アルキル基からなる群から選択されるものも挙げられる。好ましい化合物は、独立して、メチル及びエチルからなる群から選択されるものである。 Examples of the compound of the present invention include those in which R 4 , R 5 , R 6 and R 7 are independently selected from the group consisting of H and an acyclic alkyl group having 1 to 4 carbon atoms. Be done. Preferred compounds are independently selected from the group consisting of methyl and ethyl.
本発明の化合物は、ALD又はCVDのような方法を使用した薄膜堆積のための前躯体として有用となり得る。例えば、SiO2膜のALDによる蒸着を実施し得る1つの方法は、次のとおりである:
a)表面を覆う官能性O-H基を有する少なくとも1つの基材を提供する、
b)上記基材に、少なくとも1種の式1の化合物(式中、M=Si)を気相中にて送達する、
c)基材をパージガスでパージする;
d)上記基材に、酸素源を、気相中にて送達する、
e)基材をパージガスでパージする;
f)工程b)~工程e)を、所望の厚さの酸化ケイ素が堆積されるまで繰り返す。
The compounds of the present invention can be useful as precursors for thin film deposition using methods such as ALD or CVD. For example, one method of performing ALD vapor deposition of a SiO 2 film is as follows:
a) To provide at least one substrate having a functional OH group covering the surface.
b) At least one compound of the formula 1 (in the formula, M = Si) is delivered to the substrate in the gas phase.
c) Purge the substrate with purge gas;
d) Deliver an oxygen source to the substrate in the gas phase.
e) Purge the substrate with purge gas;
f) Steps b) to e) are repeated until a desired thickness of silicon oxide is deposited.
好適な酸素源としては、気相中H2O、気相中H2O2、O2、O3及びヒドラジンが挙げられるがこれらに限定されない。 Suitable oxygen sources include, but are not limited to, H 2 O in the gas phase, H 2 O 2 , O 2 , O 3 in the gas phase and hydrazine.
ALDシステムの典型的な概略図を図1に示す。 A typical schematic diagram of the ALD system is shown in FIG.
前駆体Aの反応の半分のサイクルでは、Ar等の不活性キャリアガス(1)は、制御された流量で手動弁(2)及びマスフローコントローラ(3)を通って、前駆体Aを収容するバブラー1(7)まで流れ、気化した前駆体Aを反応室(10)へと運ぶ。バブラー1用の自動切換弁(ASV)4及び8は、予め設定した時間の長さで自動的に開く。その後、ASV4及び8は自動的に閉まり、続いて反応室を、予め設定した時間の長さでパージ及び真空処理する。前駆体Aの反応の半サイクルが終了する。自動的に、ASV13及び17が開き、Ar等の不活性キャリアガス(1)は、制御された流量で手動弁(2)及びマスフローコントローラ(3)を通って、前駆体Bを収容するバブラー2(15)まで流れ、気化した前駆体Bを反応室(10)へと運ぶ。予め設定した時間の長さの後、ASV13及び17は自動的に閉まり、その後反応室を、予め設定した時間の長さでパージ及び真空処理する。前駆体Bの反応の半サイクルが終了する。全反応サイクルが終了し、すなわち、生成物の1つの原子層が基材(20)上に堆積される。このサイクルを繰り返して、所望の厚さを得る。温度は、ヒーター(18)及び熱電対(19)によって制御される。反応室内の圧力は、圧力調整弁(12)によって制御され、この弁は真空ポンプに接続している。
In half the cycle of the reaction of precursor A, the inert carrier gas (1), such as Ar, passes through the manual valve (2) and mass flow controller (3) at a controlled flow rate and is a bubbler accommodating precursor A. It flows to 1 (7) and carries the vaporized precursor A to the reaction chamber (10). The automatic switching valves (ASV) 4 and 8 for the
本発明の化合物は、当該技術分野において既知のプロセスによって調製されてもよい。以下の実施例は、かかるプロセスの例示であるが、限定することを意図するものではない。 The compounds of the present invention may be prepared by a process known in the art. The following examples are examples of such processes, but are not intended to be limiting.
(ピロロジニル)Si(OMe)3の合成
化学式:[(CH2)4N]-Si(OCH3)3
Synthesis of (pyrrolodinyl) Si (OMe) 3 Chemical formula: [(CH 2 ) 4 N] -Si (OCH 3 ) 3
7.1gのピロリジン及び100mLのヘキサンを、250mLフラスコにN2下で仕込んだ後、40mLの2.5M BuLiを加えた。1時間撹拌した後、15.2gのオルトケイ酸テトラメチルを加えた。終夜撹拌後、反応混合物を濾過し、透明な液体を回収した。揮発分を真空下で除去した。得られた液体生成物を、その後、蒸留により精製した。図2に示すように、NMR分析により、生成物を確認した。 7.1 g of pyrrolidine and 100 mL of hexane were placed in a 250 mL flask under N2 , and then 40 mL of 2.5 M BuLi was added. After stirring for 1 hour, 15.2 g of tetramethyl orthosilicate was added. After stirring overnight, the reaction mixture was filtered and the clear liquid was recovered. The volatiles were removed under vacuum. The resulting liquid product was then purified by distillation. As shown in FIG. 2, the product was confirmed by NMR analysis.
(ピロロジニル)2Si(OMe)2の合成
化学式:[(CH2)4N]2-Si(OCH3)2
(Pyrologinyl) 2 Synthetic chemical formula of Si (OMe) 2 : [(CH 2 ) 4 N] 2 -Si (OCH 3 ) 2
7.1gのピロリジン及び100mLのヘキサンを、250mLフラスコにN2下で仕込んだ後、40mLの2.5M BuLiを加えた。1時間撹拌した後、7.6gのオルトケイ酸テトラメチルを加えた。終夜撹拌後、反応混合物を濾過し、透明な液体を回収した。揮発分を真空下で除去した。得られた液体生成物を、その後、蒸留により精製した。図3に示すように、NMR分析により、生成物を確認した。図4に見られるように、TGA曲線は、残留物が極めて少ない安定な材料を示す。図5に示す蒸気圧測定は、良好な揮発性を実証し、図6は、化合物の450℃までの熱安定性を実証する。 7.1 g of pyrrolidine and 100 mL of hexane were placed in a 250 mL flask under N2 , and then 40 mL of 2.5 M BuLi was added. After stirring for 1 hour, 7.6 g of tetramethyl orthosilicate was added. After stirring overnight, the reaction mixture was filtered and the clear liquid was recovered. The volatiles were removed under vacuum. The resulting liquid product was then purified by distillation. As shown in FIG. 3, the product was confirmed by NMR analysis. As can be seen in FIG. 4, the TGA curve indicates a stable material with very little residue. The vapor pressure measurements shown in FIG. 5 demonstrate good volatility and FIG. 6 demonstrates the thermal stability of the compound up to 450 ° C.
(ピロロジニル)3Si(OMe)の合成
化学式:[(CH2)4N]3-Si(OCH3)
(Pyrologinyl) 3 Synthesis of Si (OMe) Chemical formula: [(CH 2 ) 4 N] 3 -Si (OCH 3 )
7.1gのピロリジン及び100mLのヘキサンを、250mLフラスコにN2下で仕込んだ後、40mLの2.5M BuLiを加えた。1時間撹拌した後、5.1gのオルトケイ酸テトラメチルを加えた。終夜撹拌後、反応混合物を濾過し、透明な液体を回収した。揮発分を真空下で除去した。得られた液体生成物を、その後、蒸留により精製した。図7に示すように、NMR分析により、生成物を確認した。図8に見られるように、TGA曲線は、残渣が極めて少ない安定な材料を示す。図9に示す蒸気圧測定は、良好な揮発性を実証する。 7.1 g of pyrrolidine and 100 mL of hexane were placed in a 250 mL flask under N2 , and then 40 mL of 2.5 M BuLi was added. After stirring for 1 hour, 5.1 g of tetramethyl orthosilicate was added. After stirring overnight, the reaction mixture was filtered and the clear liquid was recovered. The volatiles were removed under vacuum. The resulting liquid product was then purified by distillation. As shown in FIG. 7, the product was confirmed by NMR analysis. As can be seen in FIG. 8, the TGA curve shows a stable material with very little residue. The vapor pressure measurements shown in FIG. 9 demonstrate good volatility.
(テトラメチルグアニジニル)Si(OMe)3の合成
化学式:[NC(N(CH3)2)2]-Si(OCH3)3
Synthesis of (Tetramethylguanizinyl) Si (OMe) 3 Chemical formula: [NC (N (CH 3 ) 2 ) 2 ] -Si (OCH 3 ) 3
10gのテトラメチルグアニジン及び100mLのヘキサンを、250mLフラスコにN2下で仕込んだ後、35mLの2.5M BuLiを加えた。1時間撹拌した後、13.2gのオルトケイ酸テトラメチルを加えた。終夜撹拌後、反応混合物を濾過し、透明な液体を回収した。揮発分を真空下で除去した。得られた液体生成物を、その後、蒸留により精製した。図10に示すように、NMR分析により、生成物を確認した。 After charging 10 g of tetramethylguanidine and 100 mL of hexane into a 250 mL flask under N 2 , 35 mL of 2.5 M BuLi was added. After stirring for 1 hour, 13.2 g of tetramethyl orthosilicate was added. After stirring overnight, the reaction mixture was filtered and the clear liquid was recovered. The volatiles were removed under vacuum. The resulting liquid product was then purified by distillation. As shown in FIG. 10, the product was confirmed by NMR analysis.
(テトラメチルグアニジニル)2Si(OMe)2の合成
化学式:[NC(N(CH3)2)2]2-Si(OCH3)2
(Tetramethylguanizinyl) 2 Synthesis of Si (OMe) 2 Chemical formula: [NC (N (CH 3 ) 2 ) 2 ] 2 -Si (OCH 3 ) 2
10gのテトラメチルグアニジン及び100mLのヘキサンを、250mLフラスコにN2下で仕込んだ後、35mLの2.5M BuLiを加えた。1時間撹拌した後、6.6gのオルトケイ酸テトラメチルを加えた。終夜撹拌後、反応混合物を濾過し、透明な液体を回収した。揮発分を真空下で除去した。得られた液体生成物を、その後、蒸留により精製した。図11に示すように、NMR分析により、生成物を確認した。 After charging 10 g of tetramethylguanidine and 100 mL of hexane into a 250 mL flask under N 2 , 35 mL of 2.5 M BuLi was added. After stirring for 1 hour, 6.6 g of tetramethyl orthosilicate was added. After stirring overnight, the reaction mixture was filtered and the clear liquid was recovered. The volatiles were removed under vacuum. The resulting liquid product was then purified by distillation. As shown in FIG. 11, the product was confirmed by NMR analysis.
(テトラメチルグアニジニル)3Si(OMe)の合成
化学式:[NC(N(CH3)2)2]3-Si(OCH3)
(Tetramethylguanizinyl) 3 Synthesis of Si (OMe) Chemical formula: [NC (N (CH 3 ) 2 ) 2 ] 3 -Si (OCH 3 )
10gのテトラメチルグアニジン及び100mLのヘキサンを、250mLフラスコにN2下で仕込んだ後、35mLの2.5M BuLiを加えた。1時間撹拌した後、4.4gのオルトケイ酸テトラメチルを加えた。終夜撹拌後、反応混合物を濾過し、透明な液体を回収した。揮発分を真空下で除去した。得られた液体生成物を、その後、蒸留により精製した。 After charging 10 g of tetramethylguanidine and 100 mL of hexane into a 250 mL flask under N 2 , 35 mL of 2.5 M BuLi was added. After stirring for 1 hour, 4.4 g of tetramethyl orthosilicate was added. After stirring overnight, the reaction mixture was filtered and the clear liquid was recovered. The volatiles were removed under vacuum. The resulting liquid product was then purified by distillation.
(Et2N)Si(OMe)3の合成
化学式:[(CH3CH2)2N]-Si(OCH3)3
(Et 2 N) Synthesis of Si (OMe) 3 Chemical formula: [(CH 3 CH 2 ) 2 N] -Si (OCH 3 ) 3
3.7gのジエチルアミン及び100mLのヘキサンを、250mLフラスコにN2下で仕込んだ後、20mLの2.5M BuLiを加えた。1時間撹拌した後、7.6gのオルトケイ酸テトラメチルを加えた。終夜撹拌後、反応混合物を濾過し、透明な液体を回収した。揮発分を真空下で除去した。得られた液体生成物を、その後、蒸留により精製した。図12に示すように、NMR分析により、生成物を確認した。 3.7 g of diethylamine and 100 mL of hexane were placed in a 250 mL flask under N2 , and then 20 mL of 2.5 M BuLi was added. After stirring for 1 hour, 7.6 g of tetramethyl orthosilicate was added. After stirring overnight, the reaction mixture was filtered and the clear liquid was recovered. The volatiles were removed under vacuum. The resulting liquid product was then purified by distillation. As shown in FIG. 12, the product was confirmed by NMR analysis.
ClSi(OMe)3の合成
化学式:Cl-Si(OCH3)3
Synthesis of ClSi (OMe) 3 Chemical formula: Cl-Si (OCH 3 ) 3
250mLフラスコに、5.1gの塩化アセチル、7.6gのオルトケイ酸テトラメチル及び0.02gの三塩化アルミニウムを、N2下で仕込んだ。混合物を約3時間加熱還流し、次いで室温まで自然冷却した。揮発分を真空下で除去した。得られた液体生成物を、その後、蒸留により精製した。図13に示すように、NMR分析により、生成物を確認した。 A 250 mL flask was charged with 5.1 g of acetyl chloride, 7.6 g of tetramethyl orthosilicate and 0.02 g of aluminum trichloride under N2 . The mixture was heated to reflux for about 3 hours and then naturally cooled to room temperature. The volatiles were removed under vacuum. The resulting liquid product was then purified by distillation. As shown in FIG. 13, the product was confirmed by NMR analysis.
Cl2Si(OMe)2の合成
化学式:Cl2-Si(OCH3)2
Synthesis of Cl 2 Si (OMe) 2 Chemical formula: Cl 2 -Si (OCH 3 ) 2
250mLフラスコに、4gの(ピロロジニル)2Si(OMe)2及び50mLのジエチルエーテルを仕込み、続いて35mLの2M HCl/ジエチルエーテル溶液を添加した。1時間撹拌した後、反応混合物を濾過した。氷/アセトン浴中で冷却しながら、真空下で揮発分を濾液から除去した。図14に示すように、NMR分析により、生成物を確認した。 A 250 mL flask was charged with 4 g of (pyrologinyl) 2 Si (OMe) 2 and 50 mL of diethyl ether, followed by the addition of 35 mL of 2M HCl / diethyl ether solution. After stirring for 1 hour, the reaction mixture was filtered. Volatile components were removed from the filtrate under vacuum while cooling in an ice / acetone bath. As shown in FIG. 14, the product was confirmed by NMR analysis.
(AcO)Si(OMe)3の合成
化学式:(AcO)-Si(OCH3)3
Synthesis of (AcO) Si (OMe) 3 Chemical formula: (AcO) -Si (OCH 3 ) 3
100mLフラスコに、22.8gのオルトケイ酸テトラメチル及び15.3gの無水酢酸を、N2下で仕込んだ。混合物を120℃で約4時間加熱し、次いで室温まで自然冷却した。揮発分を真空下で除去した。次いで、分別蒸留を実施して、所望の生成物を回収した。図15に示すように、NMR分析により、生成物を確認した。 A 100 mL flask was charged with 22.8 g of tetramethyl orthosilicate and 15.3 g of acetic anhydride under N2 . The mixture was heated at 120 ° C. for about 4 hours and then naturally cooled to room temperature. The volatiles were removed under vacuum. Fractional distillation was then performed to recover the desired product. As shown in FIG. 15, the product was confirmed by NMR analysis.
(Me2N)2Si(OMe)2の合成
化学式:[(CH3)2N]2-Si(OCH3)2
(Me 2 N) 2 Synthesis of Si (OMe) 2 Chemical formula: [(CH 3 ) 2 N] 2 -Si (OCH 3 ) 2
40mLの2.5M BuLi/ヘキサン溶液を、250mLフラスコにN2下で仕込み、続いて、反応完了までジメチルアミンガスを通した。1時間撹拌した後、7.6gのオルトケイ酸テトラメチルを加えた。終夜撹拌後、反応混合物を濾過し、透明な液体を回収した。揮発分を真空下で除去した。得られた液体生成物を、その後、蒸留により精製した。図16に示すように、NMR分析により、生成物を確認した。図17に示す蒸気圧測定は、非常に良好な揮発性を実証している。図18に示す封止アンプル内で実施した熱分解試験は、この材料が450℃まで熱的に安定であることを示す。 A 40 mL 2.5 M BuLi / hexane solution was placed in a 250 mL flask under N2 and subsequently passed through dimethylamine gas until the reaction was complete. After stirring for 1 hour, 7.6 g of tetramethyl orthosilicate was added. After stirring overnight, the reaction mixture was filtered and the clear liquid was recovered. The volatiles were removed under vacuum. The resulting liquid product was then purified by distillation. As shown in FIG. 16, the product was confirmed by NMR analysis. The vapor pressure measurements shown in FIG. 17 demonstrate very good volatility. Pyrolysis tests performed in the sealed ampoule shown in FIG. 18 show that the material is thermally stable up to 450 ° C.
(ピロリジニル)2Si(OMe)2を使用したSiO2蒸着
SiO2膜を、前駆体(ピロリジン)2Si(OMe)2から、O3又はH2Oを酸化剤として使用して、様々な温度及び圧力でCVD及びALDにより作製した。SiO2膜の成長速度に関するデータを取得し、膜品質を密度及び希HF酸中でのウェットエッチング速度(WER)によって評価した。
(Pyrrolidinyl) 2 Si (OMe) 2 used in SiO 2 vapor-deposited SiO 2 film from precursor (pyrrolidin) 2 Si ( OMe ) 2 using O3 or H2O as an oxidant at various temperatures. And pressure, made by CVD and ALD. Data on the growth rate of the SiO 2 film were obtained and the film quality was evaluated by density and wet etching rate (WER) in dilute HF acid.
CVDによって作製した膜の成長速度と温度及びガス圧力の関係を図19及び20に示す。これらは、H2Oをオキシダントとして使用したときには成長速度が比較的遅く、3A/分以下(図19の目盛はnm/分単位で、これは10A/分)であることを示す。後続の試験はO3を酸化剤として使用し、図20に示すように、約10倍の成長速度が得られた。成長速度は堆積圧とはほぼ無関係で、200~300℃の温度範囲で最適化されることがわかる。 The relationship between the growth rate of the film produced by CVD and the temperature and gas pressure is shown in FIGS. 19 and 20. These indicate that the growth rate is relatively slow when H 2 O is used as an oxidant and is 3 A / min or less (the scale in FIG. 19 is in nm / min, which is 10 A / min). Subsequent tests used O3 as an oxidant , and as shown in FIG. 20, a growth rate of about 10 times was obtained. It can be seen that the growth rate is almost independent of the deposition pressure and is optimized in the temperature range of 200 to 300 ° C.
その後の試験は、1サイクル当たりの膜成長を、ALDを使用して測定した。図21は、1サイクルにつき1つの原子層堆積プロセスが正しく機能している場合に予想される通り、膜厚成長がサイクルの数に対して線形であり、曝露時間の増大とともに1サイクル当たりの成長速度が平坦になることを示す。 Subsequent tests measured membrane growth per cycle using ALD. FIG. 21 shows that the film thickness growth is linear with respect to the number of cycles, as would be expected if one atomic layer deposition process per cycle is functioning correctly, and the growth per cycle with increasing exposure time. Indicates that the speed becomes flat.
図22は、1サイクル当たりの成長速度の温度依存性を温度の関数として示し、最適温度範囲が250~400℃であることを示唆している。 FIG. 22 shows the temperature dependence of the growth rate per cycle as a function of temperature, suggesting that the optimum temperature range is 250 to 400 ° C.
生成した膜の品質を、密度及び0.1%HF酸中でのウェットエッチング速度を測定することによって評価した。図23は、250℃及び様々な堆積圧でCVDによって作製された膜のWER及び密度を示す。図24は、様々な温度でCVD及びALDによって作製した膜のWERを比較しており、ALDで作製した膜の卓越した品質を示す(より低いWERが、より優れた膜品質の指標とみなされる)。 The quality of the film produced was evaluated by measuring the density and the wet etching rate in 0.1% HF acid. FIG. 23 shows the WER and densities of films made by CVD at 250 ° C. and various deposition pressures. FIG. 24 compares the WER of films made by CVD and ALD at various temperatures and shows the excellent quality of the films made by ALD (lower WER is considered a better indicator of film quality). ).
比較のため、様々な方法で作製した膜のWERを文献から引用する。熱的SiO2のWERは、1.8A/分で測定した。これは最も高品質の薄膜であるが、多数の用途で不適合となる高温を必要とする。標準的な前駆体を用いてプラズマアシストCVD及びALDによって作製した薄膜を、それぞれ60A/分及び40A/分で測定した。図25に示すように、これらは本明細書で示したALD膜のWERよりも実質的に高い。 For comparison, the WER of films made by various methods is quoted from the literature. The WER of the thermal SiO 2 was measured at 1.8 A / min. This is the highest quality thin film, but requires high temperatures that are incompatible with many applications. Thin films made by plasma-assisted CVD and ALD using standard precursors were measured at 60 A / min and 40 A / min, respectively. As shown in FIG. 25, these are substantially higher than the WER of the ALD film shown herein.
1 不活性キャリアガス導入
2 不活性ガス導入を制御する手動弁
3 不活性ガス導入をデジタル制御するマスフローコントローラ
4 不活性キャリアガスをバブラー1に導入するための自動切換弁
5 不活性キャリアガスを導入するためのバブラー上の手動弁
6 気化した前駆体を含む不活性キャリアガスを排出するためのバブラー上の手動弁
7 前駆体Aを収容するバブラー
8 気化した前駆体を含む不活性キャリアガスを反応室に導入するための自動切換弁
9 ライン内の残留物を除去するための自動切換弁
10 反応室
11 ライン内の前駆体及び残留物を除去するための自動切換弁
12 反応室内のガス圧を制御する真空ポンプの圧力調整弁
13 不活性キャリアガスをバブラー2に導入するための自動切換弁
14 不活性キャリアガスを導入するためのバブラー上の手動弁
15 前駆体Bを収容するバブラー
16 気化した前駆体を含む不活性キャリアガスを排出するためのバブラー上の手動弁
17 気化した前駆体を含む不活性キャリアガスを反応室に導入するための自動切換弁
18 ヒーター
19 熱電対
20 基材
1 Induction of
Claims (5)
(Y) 3 -Si-(OR3)
式中:
Yは、窒素原子を介してMに結合された3~13員の複素環式基からなる群から選択され;
R3は、1~6個の炭素原子を有する環式又は非環式アルキル基である、有機金属化合物。 The organometallic compound of formula 1:
( Y ) 3 - Si- (OR 3 )
During the ceremony :
Y is selected from the group consisting of 3 to 13 member heterocyclic groups bonded to M via a nitrogen atom;
R 3 is an organometallic compound which is a cyclic or acyclic alkyl group having 1 to 6 carbon atoms.
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CA2920646A1 (en) | 2017-08-12 |
JP7265589B2 (en) | 2023-04-26 |
WO2017136945A1 (en) | 2017-08-17 |
KR20180116308A (en) | 2018-10-24 |
JP2021181621A (en) | 2021-11-25 |
JP2019507750A (en) | 2019-03-22 |
CN109588049A (en) | 2019-04-05 |
SG11201806724YA (en) | 2018-09-27 |
US11802134B2 (en) | 2023-10-31 |
EP3414254A4 (en) | 2019-10-23 |
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